Surfactant and dispersible or emulsifiable compositions employing surfactant

ABSTRACT

A surfactant comprising a carboxylic acid ester or amide carrying a terminal strong acid group selected from carboxymethyl, sulphate, sulphonate, phosphate and phosphonate, suitable for stabilising dispersions of solids in organic liquids and oil/water emulsions, processes for the preparation of the surfactant and dispersions and emulsions containing the surfactant. A preferred species of the surfactant is a poly(hydroxyalkanecarboxylic acid) having the strong acid group attached, either directly or through a linking group, to a terminal hydroxy or carboxylic acid group.

This is a division of application Ser. No. 07/070,676, filed Jul. 6,1987, now U.S. Pat. No. 5,300,255, which is a continuation ofapplication Ser. No. 06/707,473, filed Mar. 1, 1985, now abandoned.

This specification describes an invention relating to a compound havingutility as a surfactant, to a composition of a solid or an organicliquid and the surfactant, to a dispersion of a solid in an organicliquid containing the surfactant and to an aqueous emulsion containingthe surfactant.

The Surfactant

According to a first aspect of the present invention there is provided acompound comprising a carboxylic acid ester or amide carrying a terminalacid group selected from carboxymethyl, sulphate, sulphonate, phosphateand phosphonate, hereinafter referred to as the "acid group". Thecarboxylic acid ester or amide is preferably an oligo- or poly-estercomprising from 2 to 100 units of one or more hydroxycarboxylic acidmonomers.

The term carboxymethyl, that is a group of the formula --CH₂ COO⁻, doesnot include a carboxymethyl group in which the CH₂ group is directlyattached to a carbon atom of an unsubstituted hydrocarbon chaincontaining two or more carbon atoms.

A preferred compound in accordance with the present invention conformsto the general formula:

    A--(O--B--CO).sub.m --D                                    I

wherein A and D are are groups one of which is or carries the acid groupas hereinbefore defined and the other is a convenient terminal groupwhich does not render the compound hydrophilic, B is a hydrocarbon groupand m is from 1 to 100.

In the compound of Formula I, when D carries the acid group, A ispreferably the residue (A¹ --CO--) of an esterifiable carboxylic acid ofthe formula A¹ --COOH, in which A¹ is H, a hydrocarbon or a substitutedhydrocarbon. Although A¹ is conveniently an optionally substitutedalkyl, alkenyl, cycloalkyl or polycycloalkyl group containing up to 50,more preferably up to 35, carbon atoms, it can be any convenientmonovalent group. In this case D is preferably a polyvalent, morepreferably di- or tri-valent, bridging group linking the acid group tothe ester chain, A¹ CO(O--B--CO)_(m) --, e.g. a group such as D² definedbelow. Where D has a valency greater than 2 it may link two or more acidgroups to a single ester or two or more esters chain to a single acidgroup. Where the acid group has more than one valency it may be linkedto two or more esters through two bridging groups.

In the compound of Formula I, when A carries the acid group, D ispreferably the residue of an alcohol, a thiol or a primary or secondaryamine, D¹ --XH, in which D¹ is an aliphatic or alicyclic group ofsimilar character to A¹, and X is O, S or NR in which R is H, alkyl,alkenyl, cycloalkyl, or phenyl, in which the alkyl and alkenyl groupscontain up to 20 carbon atoms and the cycloalkyl groups from 4 to 8carbon atoms. In this case A is preferably the acid group itself andwhere this has more than one valency it may be linked to two or morepolyester chains, although A may also be a polyvalent linking group,like D above, linking the acid group to the polyester chain. Thehydrocarbon group represented by B, which is preferably an optionallysubstituted alkyl, alkenyl, cycloalkyl or polycycloalkyl group,preferably contains up to 50, more preferably from 3 to 24, carbonatoms, with at least 3 carbon atoms directly between the --O-- and--CO-- groups. Optional substitutents for A¹, D¹ and B include halo,especially chloro, hydroxy, amino, alkoxy and other non-ionic species inso far as they do not make the ester/amide chain hydrophilic incharacter.

It is preferred that m is from 2 to 75, more preferably 3 to 30, so thatthe compound of Formula I is an oligo- or poly-ester. Where m=1 it ispreferred that the group represented by A or D which is remote from theacid group contains at least 6 carbon atoms and that the surfactantcontains at least 12 carbon atoms and more preferably at least 20 carbonatoms.

A first preferred species of the first aspect of the present invention,particularly suitable for use as a surfactant in compositions comprisingan oil phase and an aqueous phase, is a compound which comprises ahydrophobic component and a hydrophilic component covalently bondedtogether, wherein the hydrophobic component is the residue of anoligomeric or polymeric monocarboxylic acid of the formula: ##STR1## inwhich

A² is hydrogen or a monovalent hydrocarbon or substituted hydrocarbongroup;

B¹ is hydrogen or a monovalent C₁ to C₂₄ hydrocarbon group;

B² is a divalent C₁ to C₂₄ hydrocarbon group;

n is zero or 1; and

p is zero or an integer up to 100, preferably 2 to 20,

and wherein the hydrophilic component contains an anionic groupingselected from phosphate, phosphonate, sulphate, sulphonate andcarboxymethyl, i.e. the acid group.

The acid group in the first preferred species may be in the free acidform or as a salt thereof with a base, for example, ammonia, organicbases such as amines and aminoalcohols, and inorganic bases.

The term "oil phase" and "oil" used in respect of the first species andcompositions based thereon refers to water-immiscible, preferablynon-polar, liquids in general. It is not limited to, though embracing,naturally occurring oils such as hydrocarbons and fatty acid esters.

Where the surfactant of Formula II is designed for use in compositions,particularly oil-water emulsions, containing non-polar organic liquidsthe compound of Formula II is preferably oil-soluble, that is the oilphase of the composition should be better than a theta solvent for thecompound. The significance of the expression "theta solvent" isdiscussed in "Polymer Handbook" (Ed. Brandrup & Immergut, Interscience,1966) at pages IV 163-166. Briefly, this definition implies that in asolution of a polymer in a solvent, a solvent which is better than atheta solvent for the polymer, the polymer exists in anon-self-associated condition. The definition is usually satisfied byany liquid which would normally be described as a "good" solvent for thepolymer. Considerable variation in the composition of the compound ofFormula I, particularly in respect of the nature of the groups A², B¹and B², is possible whilst meeting the requirement that the compoundshould be oil-soluble in the above sense. Generally speaking, the morethe oil phase of the composition tends towards a fully aliphaticcharacter, the longer will the hydrocarbon chains of these groups needto be.

A second preferred species of the of the first aspect of the presentinvention is a compound conforming to the formula:

    [A.sup.3 --CO--(O--B.sup.3 --CO).sub.m --D.sup.2 ].sub.k --L MIII

wherein

A³ --CO is the residue of an esterifiable carboxylic acid of theformula, A³ --COOH;

B³ is selected from alkylene, alkenylene, cycloalkylene,polycycloalkylene and halo derivatives thereof;

D² is a bridging group of the formula --X--G--Y-- wherein X is O, S orNR and Y is O, NR or a direct link, in which each R independently is ashereinbefore defined or, where X and Y are both NR, the two groups, R,may form a single alkylene or alkenylene group linking the two nitrogensto which they are attached, and G is alkylene, alkenylene, cycloalkyleneor arylene;

L is phosphonate, sulphonate or methylenecarboxylate;

M is a cation;

k is 1 or 2;

and m is as hereinbefore defined.

A third preferred species of the first aspect of the present inventionis a compound conforming to the formula:

    [D.sup.1 --X--(CO--B.sup.3 --O).sub.m ].sub.k --L M        IV

wherein D¹ is an aliphatic or alicyclic group and B³, L, M, X, m and kare as hereinbefore defined.

The residue of the esterifiable carboxylic acid represented by A³ CO inFormula III may be any convenient terminal hydrophobic group for theester chain, --(O--B³ --CO)_(m), although it is preferably an optionallysubstituted alkyl, alkenyl, cycloalkyl or polycycloalkyl groupcontaining up to 50 carbon atoms and more preferably from 1 to 35 carbonatoms. The optional substituents are preferably selected from hydroxy,amino, halogen and alkoxy provided A³ retains its hydrophobic character.

The aliphatic or alicyclic group represented by D¹ in Formula IV ispreferably an optionally substituted alkyl, alkenyl, cycloalkyl orpolycycloalkyl group containing up to 35 carbon atoms, the optionalsubstituents being preferably selected from halogen, tertiary amino andalkoxy.

The alkylene, alkenylene, cycloalkylene and polycycloalkylene groupsrepresented by B³ preferably contain from 3 to 35 carbon atoms, morepreferably from 5 to 20 carbon atoms, with at least 3 and morepreferably at least 5 carbon atoms between the --O-- and --CO-- groups,and are preferably unsubstituted.

The alkylene and alkenylene groups represented by G preferably containup to 10 carbon atoms and more preferably from 2 to 6 carbon atoms. Thecycloalkylene group represented by G preferably contains from 4 to 8carbon atoms and especially preferably is 1,4-cyclohexylene. The arylenegroup represented by G is preferably monocyclic and especially1,4-phenylene.

The alkyl and alkenyl groups represented by R may contain up to 25carbon atoms and preferably contain up to 5 carbon atoms. Where twogroups, R, form a single group this preferably contains up to 10 carbonatoms.

In the compound of Formula III in which Y is O the acid group, L, isattached to the ester/amide chain through an oxygen atom so thatphosphonate and O form phosphate and sulphonate and O form sulphate.Similarly, where Y is NR, phosphonate and NR form phosphorimide andsulphonate and NR form sulponamide.

The cation represented by M is preferably H⁺, a metal ion, an ammoniumion or a substituted ammonium ion and examples of suitable cations areNa⁺, K⁺, Ca²⁺, NH₄ ⁺, N(CH₃)₄ ⁺ and NH(CH₃)₄ ⁺.

Specific examples of the bridging group represented by D² are --NHC₂ H₄--, --OC₂ H₄ --, --OC₂ H₄ O--, --OC₂ H₄ NH--, --NH(CH₂)_(n) NH--,wherein n is from 2 to 5, piperazin-1,4-ylene andphen-1,4-ylene-diamino.

Examples of the groups represented by A¹, A² and A³ are methyl, ethyl,CH₃ (CH₂)₄ --, CH₃ (CH₂)₁₀ --, CH₃ (CH₂)₁₄ --, CH₃ (CH₂)₁₆ --, HO(CH₂)₅--, CH₃ (CH₂)₇ CH═CH(CH₂)₇ --, CH₃ (CH₂)₂₈ --, CH₃ (CH₂)₅ CH(OH)(CH₂)₁₀--, CH₃ (CH₂)₄ CH═CHCH₂ CH═CH(CH₂)₇ --, CH₃ (CH₂)₅ CH(OH)CH₂ CH═CH(CH₂)₇-- and CH₃ OCH₂ -- and the residue of abietic acid i.e. the radicalderived from abietic acid by removal of the carboxyl group.

Examples of the group represented by D¹ are methyl, ethyl, CH₃ (CH₂)₉--, CH₃ (CH₂)₁₁ --, CH₃ (CH₂)₁₅ --, CH₃ (CH₂)₁₇ --, CH₃ (CH₂)₂₉ --, CH₃(CH₂)₇ CH═CH(CH₂)₇ --, CH₃ OCH₂ --, CH₃ (CH₂)₄ CH═CHCH₂ CH═CH(CH₂)₇ --and the residue of abietyl alcohol, i.e the radical derived from abietylalcohol by removal of the OH group.

Examples of the groups represented by B and B³ are: ##STR2## and--(CH₂)₅ --.

Examples of the groups represented by B¹ are H, C₆ H₁₃, C₈ H₁₇ and C₉H₁₉ and by B² are --CH--(CH₂)₁₀ --, --CH--(CH₂)₈ --, --CH--(CH₂)₇ --,and --CH--CH₂ CH═CH(CH₂)₇ --.

Compositions Containing the Surfactant

The compounds of the first aspect of the invention, hereinafter referredto as "surfactants" are particularly useful for enhancing thedispersibility of solids in organic media and for stabilisingwater-in-oil and oil-in-water emulsions.

(i) First Composition

According to a second aspect of the present invention there is provideda composition of a solid and a surfactant according to the first aspectof the invention. The surfactant for use in the first composition ispreferably a compound in accordance with Formula III or Formula IV.

The composition of the second aspect, hereinafter referred to as the"first composition", may comprise an intimate mixture of the twocomponents but preferably comprises a coating of the surfactant onfinely divided primary particles of the solid which preferably have amean diameter below 10 microns and more preferably below 5 microns. Thecomposition may be dry, in which case the primary particles may beaggregated, or it may be in the form of a dispersion of the solid in anorganic medium, preferably one which is a liquid, or is at leastplastic, under normal ambient conditions.

The solid may be any material which it is desired to stabilise in afinely divided state in an organic medium. Examples of suitable solidsare pigments for solvent inks and paints; pigments and fillers forplastics materials; dyestuffs, optical brightening agents and textileauxiliaries for solvent dyebaths, inks and other solvent applicationsystems; magnetic solids, especially magnetic metals or alloys andmagnetic oxides, for use in the production of magnetic tapes and discs,solids for oil-based and invert-emulsion drilling muds, dirt and soilparticles in dry cleaning fluids and biocides, agrochemicals andpharmaceuticals which are applied as dispersions in organic media.

The first composition, whether dry or in the form of a dispersion maycontain other ingredients, such as resins, binders, fluidising agents,anti-sedimentation agents, plasticisers and preservatives.

A preferred solid is a pigment from any of the recognised classes ofpigments described, for example, in the Third Edition of the ColoursIndex (1971) and subsequent revisions of, and supplements thereto, underthe chapter headed "Pigments".

Examples of inorganic pigments are titanium dioxide, zinc oxide,Prussian blue, cadmium sulphide, iron oxides, vermillion, ultramarineand the chrome pigments, including chromates, molybdates and mixedchromates and sulphates of lead, zinc, barium, calcium, and mixtures andmodifications thereof which are commercially available asgreenish-yellow to red pigments under the names primrose, lemon, middle,orange, scarlet and red chromes.

Examples of organic pigments are those from the azo, disazo, condensedazo, thioindigo, indanthrone, isoindanthrone, anthraquinone,anthanthrone, isodibenzanthrone, triphendioxazine, phthalocyanine,especially copper phthalocyanine and its nuclear halogenatedderivatives, and quinacridone series and also lakes of acid, basic andmordant dyes. Carbon black, although strictly inorganic, behaves morelike an organic pigment in non-aqueous dispersions. Preferred organicpigments are phthalocyanines, and especially copper phthalocyanines,monoazos, disazos, indanthrones, anthanthrones, quinacridones and carbonblacks.

Where the solid is a pigment the first composition is compatible withthe fluidising agents disclosed in UK Patent Specifications Nos 1508576and 2108143. The fluidising agent described in UK 1508576 is asubstituted ammonium salt of a coloured acid wherein there are from 19to 60 carbon atoms in at least 3 chains attached to the N atom of thesubstituted ammonium ion. The fluidising agent described in UK 2108143is a water-insoluble disazo compound comprising a central divalent groupfree from acidic and other ionic substituents linked, through azogroups, to two monovalent end groups, one end group being free fromacidic and other ionic substituents and the other carrying a singlesubstituted ammonium salt group. Such fluidising agents are useful forenhancing the fluidity of the dispersion form of the first composition.

Examples of magnetic solids include gamma-Fe₂ O₃, cobalt-doped gamma-Fe₂O₃, magnetite, CrO₂, Ferrites and particulate iron, cobalt and nickel,and alloys thereof.

Examples of agrochemicals include the fungicides flutriafen,carbendazim, chlorothalonil and mancozeb.

The organic medium may be any organic medium in which it is desired todisperse the solid and with which the surfactant is compatible and atleast partially soluble. It is preferably liquid, or at least plastic,at normal ambient temperatures. Examples of suitable media arehydrocarbons and chlorinated hydrocarbons, such as aliphatic petroleumfractions, chloroform, carbon tetrachloride, perchloroethylene, benzene,toluene, xylene and chlorobenzene, alcohols such as n-butanol, etherssuch a di-alkylethers and tetrahydrofuran, ketones such asmethyl-ethyl-ketone, methyl-i-butyl ketone and cyclohexanone and esterssuch as butyl acetate and 2-ethoxyethyl acetate. Mixtures of theseliquids may be used and, in general, the organic liquid or mixture isselected to meet the requirements of the end-use to which thecomposition will be put.

The first composition may be prepared by mixing the components or thesurfactant may be added to the solid during the preparation of thelatter, preferably during the later or finishing stages of preparation.The first composition may also be prepared by subjecting a mixture ofthe solid, the surfactant, preferably in the organic medium to agrinding operation sufficient to reduce the particle size of the solidto below 10 microns. If the composition includes a liquid organicmedium, this may be subsequently removed, e.g. by evaporation, if thecomposition is required in a dry form.

The first composition preferably contains from 1% to 100% by weight ofthe dispersing agent, based on the weight of the solid, but morepreferably contains from 1% to 30%, on the same basis. In the dispersionform, the first composition preferably contains from 10% to 90% byweight of the solid the precise quantity depending on the nature of thesolid and the relative densities of the solid and liquid. For example,dispersions of organic pigments preferably contain from 15% to 60% byweight of pigment whereas dispersions of an inorganic pigmentspreferably contain from 40% to 90% of the pigment, based on the totalweight of the composition.

(ii) Second and Third Compositions

According to a third aspect of the present invention there is provided acomposition of a surfactant, in accordance with the first aspect of theinvention, and a water-immiscible organic liquid, hereinafter referredto as the "second composition". The second composition may comprise theorganic liquid and the surfactant alone or it may be converted to athird composition comprising a water-in-oil or oil-in-water emulsion ofthe organic liquid and an aqueous medium stabilised with the surfactant.Such an emulsion forms a fourth aspect of the present invention.

Water-immiscible organic liquids which may be satisfactorily emulsifiedin water with the aid of these surfactants include fatty glycerides,mineral oils, hydrocarbon fuel oils and other liquid hydrocarbons,synthetic lubricants such as the tetra-pelargonate ester ofpentaerythritol, bitumens, waxes and polyolefins such aspoly(isobutylene). The resulting emulsions are useful, inter alia ashydraulic fluids, cutting oils and other metal-working fluids.

A preferred surfactant for use in the second composition is a compoundin accordance with Formula II.

In producing the emulsions, it is generally preferred to add thesurfactant to the oil phase before the latter is contacted with theaqueous phase. In cases where it is desired to neutralise the freeacidic groups in the surfactant, the base may be introduced before,during or after the blending of the surfactant with the oil phase.

The surfactants of the invention, especially those of Formula II, areadvantageous in that they can tolerate water phases which are high indissolved inorganic content, for example naturally hard waters or brinescontaining up to saturation levels of salts such as sodium chloride,magnesium chloride or calcium chloride. Those surfactants in which theanionic grouping is derived from phosphoric acid have particularly goodtolerance towards the presence of polyvalent cations such as Ca²⁺. Afurther advantage is that the surfactants do not lose their efficacy athigher temperatures; they perform satisfactorily at temperatures of upto 100° C. or higher.

The proportion of surfactant which is required in a particular oil/watersystem may vary widely according to the nature of the two phases, but inmost instances it will lie in the range 0.1% to 25% by weight, based onthe disperse phase of the emulsion.

Preparation of Surfactants

The surfactants of the first aspect of the invention may be prepared byreaction between a polyester having a terminal carboxylic acid and/orhydroxy group and a compound having group reactive therewith andcarrying a terminal acid group. Alternatively the polyester may bereacted directly with a precursor of the acid group or with abifunctional compound which is subsequently reacted with a precursor ofthe acid group. Preferred polyesters are those derived fromhydroxycarboxylic acids or lactones, such as 12-hydroxystearic acid andE-caprolactone. In the above processes, a monomeric precursor of thepolyester may be used in place of the prepared polyester, whereby thepolyester is formed in situ and directly converted into the surfactant.Suitable precursors of the polyester are hydroxycarboxylic acids andlactones. Suitable compounds containing the acid group are alpha-amino-or alpha-hydroxy-alkane carboxylic acids, such as glycine and glycollicacid and amino- and hydroxy-organic sulphonic or phosphonic acids, suchas aminoethane sulphonic acid, suitable precursors of the acid group arephosphorus pentoxide and sulphonyl chloride and suitable bifunctionalcompounds, which can form a linking group between the polyester and theacid group, are polyamines, polyols and hydroxyamines.

(i) Surfactant of First Preferred Species

The oil-soluble monocarboxylic acid of Formula II, the residue of whichforms the hydrophobic component of the first preferred species of thefirst aspect of the invention, may be prepared by theinteresterification of one or more monohydroxymonocarboxylic acidstogether with a monocarboxylic acid free from hydroxyl groups which actsas a chain terminator. The hydrocarbon chains A², B¹ and B² may belinear or branched. A² is preferably an alkyl group containing up to 25carbon atoms, for example a straight-chain C₁₇ H₃₅ -group derived fromstearic acid. B¹ is preferably a straight-chain alkyl group, and B² ispreferably a straight-chain alkylene group; for example, the unitcontaining B¹ and B² may be derived from 12-hydroxy-stearic acid.

The hydroxyl group in the monohydroxymonocarboxylic acid, and thecarboxyl group in either carboxylic acid, may be primary, secondary ortertiary in character. Suitable hydroxycarboxylic acids for use in thefirst stage include glycollic acid, lactic acid, hydracrylic acid,6-hydroxycaproic acid, ricinoleic acid and, more especially12-hydroxystearic acid. The non-hydroxylic carboxylic acid which acts asa chain terminator, and hence as a means of regulating the molecularweight of the complex monocarboxylic acid, may be, for example, aceticacid, propionic acid, caproic acid, stearic acid or an acid derived froma naturally occurring oil, such as tall oil fatty acid. Commercialquantities of 12-hydroxystearic acid normally contain up to 15% ofstearic acid, and other non-hydroxy acids as impurities and canconveniently be used without further admixture to produce a polymer ofmolecular weight about 1500-2000. Where the non-hydroxylicmonocarboxylic acid is separately introduced, the proportion which isrequired in order to produce a polymer or oligomer of a given molecularweight can be determined either by simple experiment or by calculation.

The interesterification of the monohydroxymonocarboxylic acid and thenon-hydroxylic monocarboxylic acid may be effected by heating thestarting materials in a suitable hydrocarbon solvent such as toluene orxylene, which is able to form an azeotrope with the water produced inthe esterification reaction. The reaction is preferably carried out inan inert atmosphere, e.g. of nitrogen, at a temperature of up to 250°C., conveniently at the refluxing temperature of the solvent. Where thehydroxyl group is secondary or tertiary the temperature employed shouldnot be so high as to lead to dehydration of the acid molecule. Catalystsfor the esterification, such as p-toluene sulphonic acid, zinc acetate,zirconium naphthenate or tetrabutyl titanate, may be included, with theobject of either increasing the rate of reaction at a given temperatureor of reducing the temperature required for a given rate of reaction.

The hydrophobic component mentioned above may conveniently be linked tothe hydrophilic component by reacting the compound of Formula II withone or more appropriate co-reactants capable of reacting with the freecarboxyl group therein. The carboxyl group reacts readily with compoundscontaining, for example, hydroxyl or amino groups and therefore one wayin which the surfactants of the invention may be made is by reacting thecompound of Formula II with a compound which has in the molecule atleast one hydroxyl or amino group and also at least one acid group.Examples of such compounds, where the acid group present in thehydrophilic component of the surfactant is a carboxyl group, includeamino-acids such as glycine and short-chain hydroxy acids such asglycollic acid or lactic acid.

Another way in which the surfactants may be produced is by an indirect,two-stage process in which the compound of Formula II is reacted with alinking compound containing at least one reaction group such as ahydroxyl or amino group and at least one other reactive group, and theintermediate product so obtained is then reacted with a compoundcontaining the acid group and a group capable of combining with theother reactive group in the linking compound. Suitable linking compoundsinclude polyols, polyamines and hydroxyamines, as examples of whichthere may be mentioned ethylene glycol, propylene glycol, glycerol,trimethylol propane, pentaerythritol, sorbitol, ethylene diamine,trimethylene diamine, hexamethylene diamine, diethylene triamine,ethanolamine, diethanolamine, dipropanolamine andtris(hydroxymethyl)aminomethane. Hydroxyamines are appropriate linkingcompounds since, because of the difference in reactivity of the hydroxyland amino groups, it is easier to avoid the formation of double-ended oroligomeric intermediate products. Suitable compounds containing the acidgroup and another reactive group, with which the intermediate productsare then reacted, include strong inorganic acids such as phosphoricacid, sulphuric acid, chlorosulphonic acid and sulphamic acid, andorganic acids such as alkyl- and aryl-phosphonic acids, alkyl- andaryl-sulphonic acids and monochloracetic acid.

In preparing the surfactant from the compound of Formula II the reactionof the latter with the compound containing the acid group (in the directroute) or with the linking compound (in the indirect route) is carriedout under conditions which are appropriate for the reactants involved.Thus, in the case where the compound of Formula II is reacted directlywith a functional acid such as glycine or glycollic acid the reactantsmay be heated together at a temperature in the range 180°-260° C., ifdesired in the presence of a solvent such as xylene and optionally alsoin the presence of a catalyst such as zirconium octoate or tetrabutyltitanate, until the acid value of the mixture has fallen to theappropriate level. The reactants are used in approximatelystoichiometric proportions with respect to the carboxyl group in thecompound of Formula II and the hydroxyl or amino group in the compoundbearing the acid group. Similar conditions apply, in the case of theindirect route, to the reaction between the compound of Formula II andthe linking compound, except that only one reactive group in the latteris taken into account in order to ensure that the intermediate productstill contains at least one grouping available for subsequent reactionwith the compound bearing the acid group. Where the linking compound isa hydroxyamine, a reaction temperature in the range 150°-200° C. maysuffice. Here again, an inert solvent or diluent and/or a catalyst maybe present if desired.

In the second stage of the indirect route, the intermediate product isreacted with the compound containing the acid group at a temperature andfor a period of time sufficient for completion of the reaction asindicated by the attainment of a substantially constant acid value ofthe reaction mixture. Where the compound containing the acid group is apolybasic acid such as phosphoric acid or sulphuric acid, it ispreferred that only one of the ionisable hydrogen atoms therein isreacted and that no attempt is made to remove water of reaction; it isfound that reaction for about 3 hours at a temperature in the range40°-70° C. is usually adequate, more stringent conditions introducingthe risk of dehydration of the product, especially where sulphuric acidis used. These complications do not arise in the case of monochloraceticacid, but the reaction proceeds more slowly and rather more forcingconditions may be required. In general, the compound containing the acidgroup is used in an approximately stoichiometric amount with respect tothe available reactive groups in the intermediate product (taking intoaccount the above-mentioned preference in the case of a polybasic acid),but a lower or higher amount than this may be used if desired.

The final products of the preparative procedures outlined above are allacidic in character and may, if desired, be stored and used assurfactants in that form. They may, however, alternatively beneutralised with ammonia, organic bases such as amines or aminoalcohols,or inorganic bases before storage or use.

(ii) Surfactant of Formula III

The surfactant of Formula III, in which Y is a direct link, may beprepared by reaction of a polyester having a terminal carboxylic acidgroup with an amino- or hydroxy-organic sulphonate or phosphonate, andpreferably an amino- or hydroxy-alkyl sulphonate or phosphonate. Thesurfactant of Formula III in which Y is NR¹ or oxygen, can be preparedby reaction of the same polyester with a diol, a diamine or with anaminoalcohol and subsequently reacting the intermediate formed in thefirst stage with a phosphating agent, such as phosphorus pentoxide, or asulphating agent, such as chlorosulphonic acid.

According to a fifth aspect of the present invention there is provided aprocess for the preparation of a compound according to Formula III,wherein Y is a direct link, which comprises reacting a polyester of theformula

    A.sup.3 --CO--(O--B.sup.3 --CO).sub.m --OH                 V

with a compound of the formula:

    (H--X--G).sub.k --L M                                      VI

wherein A³, B³, X, G, L, M, k and m have the same meanings as in FormulaIII.

According to a sixth aspect of the present invention there is provided aprocess for the preparation of a compound according to Formula III inwhich Y is O or NR which comprises reacting a polyester of Formula Vwith a compound of the formula:

    H--X--G--Y--H                                              VII

and subsequently with a sulphating or phosphating agent.

In a modification of the processes forming the fifth and sixth aspectsof the present invention the compound of Formula VI or Formula VII isadded to the precursors of the polyester of Formula V, i.e. a mixture ofthe compounds A³ --COOH and HO--B³ --COOH or the lactone of HO--B³--COOH, under polymerising conditions, whereby the polyester of FormulaV is formed in situ and is converted directly into the compound ofFormula III.

(iii) Surfactant of Formula IV

The surfactant of Formula IV may be prepared by polymerising ahydroxycarboxylic acid or lactone in the presence of a monohydricalcohol, or a primary or secondary mono-amine, to form a polyesterhaving a terminal hydroxy group and reaction of the hydroxy-terminatedpolyester with a phosphating, such as phosphorus pentoxide or asulphating agent, such a chlorosulphonic acid.

According to a seventh aspect of the present invention there is provideda process for the preparation of a compound according to Formula IVwhich comprises polymerising a hydroxycarboxylic acid of the formula:

    HOOC--B.sup.3 --OH                                         VIII

or a lactone thereof, in the presence of a monohydric alcohol of theformula, D¹ OH or a primary or secondary amine of the formula D¹ NH₂ orD¹ RNH, and reacting the product with a phosphating or sulphating agentwherein B³, D¹ and R are as hereinbefore defined.

EXAMPLES OF THE INVENTION

The invention is further illustrated by the following examples in whichall parts and percentages are by weight unless otherwise indicated.

Intermediate 1

This is poly(12-hydroxystearic acid) having an acid value of 35 mg.KOH/gprepared by the process for "Polyester A" in UK Patent Specification No1,373,660.

Intermediate 2

A mixture of 3206 g of ricinoleic acid and 6 g of tetrabutyl titanatewas stirred at 170°-175° C. under a stream of inert gas. The acid valueof the reaction mixture was determined at intervals and after 17 hours,when the acid value was 34 mg.KOH/g, reaction was stopped by cooling thereaction mixture to room temperature. The product is hereinafter calledIntermediate 2.

Intermediate 3

A mixture of 500 g of E-caprolactone, 67 g of dodecanol and 0.1 g oftetrabutyl titanate was stirred at 160°-180° C. under a stream ofnitrogen for 19 hours. The reaction mass was then discharged and allowedto solidify to a waxy solid, hereinafter referred to as Intermediate 3.

Intermediate 4

This was prepared in the same manner as Intermediate 3 except that thequantity of dodecanol was reduced to 32.6 g and the reaction time wasreduced to 6 hours. The waxy product is hereinafter referred to asIntermediate 4.

Intermediate 5

This was prepared in the same manner as Intermediate 3 except that thequantity of dodecanol was reduced to 16.0 g and the reaction time wasreduced to 6 hours. The waxy product is hereinafter referred to asIntermediate 5.

Intermediate 6

A mixture of 2968.8 g of commercial 12-hydroxystearic acid and 325.5 gof xylene was charged to a round-bottom flask fitted with a stirrer anda Dean and Stark separator. With an atmosphere of nitrogen beingmaintained throughout, the mixture was heated with stirring to refluxtemperature (180°-190° C.) and kept at that temperature for about 1hour, with the addition of more xylene if necessary to ensure removal ofwater of condensation. With the source of heat temporarily removed,there was then added, into the middle of the reaction mixture by meansof a pipette, 5.61 g of tetrabutyl titanate and heating under reflux wasresumed until the acid value of the mixture had fallen to the range30-36 mg KOH/g. The product had a solids content of 90.1% and ishereinafter referred to as Intermediate 6.

Intermediate 7

This was prepared in the same manner as Intermediate 3 except that thequantities of E-caprolactone and dodecanol used were 250 g and 51 grespectively. The waxy product is hereinafter referred to asIntermediate 7.

Intermediate 8

This was prepared in the same manner as Intermediate 3 except that thequantities of E-caprolactone and dodecanol used were 250 g and 90 grespectively. The soft waxy product is hereinafter referred to asIntermediate 8.

Intermediate 9

This was prepared in the same manner as Intermediate 3 except that thequantities of E-caprolactone and dodecanol used were 22.6 g and 100 grespectively. The very soft waxy product is hereinafter referred to asIntermediate 9.

Intermediate 10

A mixture of 153 g of E-caprolactone, 87 g of n-octanol and 0.1 g oftetrabutyl titanate was stirred at 160°-180° C. under a stream ofnitrogen for 10 hours. The reaction mass was then discharged, and ishereinafter referred to as Intermediate 10.

Intermediate 11

A mixture of 355 g of E-caprolactone, 50 g of dodecylamine and 0.1 g oftetrabutyl titanate was stirred at 170°-180° C. under a stream ofnitrogen for 8 hours. The reaction mass was then discharged, and ishereinafter referred to as Intermediate 11.

Fluidising Agent 1

This is the product described as Agent B in UK 1,508,576.

EXAMPLE 1

Solution A was prepared by mixing 26.4 g of a 48.6% aqueous sodiumhydroxide solution and 100 g of water, and then dissolving 39 g ofaminoethane sulphonic acid in the mixture.

Solution B was prepared by mixing 500 g of Intermediate 1 and 43 gtoluene until the mixture was homogeneous.

Solution B was transferred to a flask equipped with a gas inlet tube anda Dean and Stark water separator. Solution A was added to the flask over5 minutes while the contents were stirred rapidly. Stirring wascontinued while heating was applied, and initially all the water wasremoved in the Dean and Stark separator. Toluene was then distilled offuntil the temperature of the reaction mass rose to 180° C. The reactionmass was then stirred at 180°-190° C. for 5 hours under a stream ofinert gas, after which the reaction was stopped by cooling the reactionmixture to room temperature. The reaction product, hereinafter calledSurfactant 1, had an acid value of 7.4 mg.KOH/g.

EXAMPLE 2

This preparation was carried out in exactly the same way as Example 1,except that Solution A was prepared from 2.5 g of a 48.6 w/w % aqueoussodium hydroxide solution, 25 g of water and 3.8 g of aminoethanesulphonic acid, and Solution B was prepared from 50 g of Intermediate 2and 21.7 g of toluene.

The final stage of the reaction was carried out at 180° C. for 51/2hours. The reaction product, hereinafter called Surfactant 2 had an acidvalue of 5.9 mg.KOH/g.

EXAMPLE 3

Solution A was prepared by mixing 7.58 g of a 46.6% aqueous sodiumhydroxide solution and 19.9 g of water then dissolving 12.5 g ofaminoethane sulphonic acid in the mixture.

Solution B was prepared by mixing 136.8 g of E-caprolactone and 21.7 gtoluene until the mixture was homogeneous.

Solution B was transferred to a flask equipped with a gas inlet tube anda Dean and Stark water separator. Solution A was added to the flask over5 minutes while the contents were stirred rapidly. Stirring wascontinued while heating was applied, and initially all the water wasremoved in the Dean and Stark separator. At this stage some solid wasdeposited on the sides of the flask. Toluene was then distilled offuntil the temperature of the reaction mass rose to 180° C., and duringthis period the solid re-dissolved giving a homogeneous reaction mass.The mass was then stirred for 7 hours at 170°-190° C. under a stream ofinert gas, after which the reaction was stopped by cooling the reactionmixture to room temperature. Infra-red spectroscopy showed that almostno unreacted E-caprolactone was then present. The reaction product was awaxy solid, hereinafter called Surfactant 3.

EXAMPLE 4

317 g of Intermediate 3 was stirred at 60°-65° C. and 10 g of phosphoruspentoxide was then added gradually over 30 minutes. The temperature wasthen raised to 90° C., and the reaction mass stirred for a further 16hours at this temperature. It was then discharged and allowed tosolidify to give a waxy solid, hereinafter called Surfactant 4.

EXAMPLE 5

The process of Example 4 was repeated except that the 317 g ofIntermediate 3 was replaced by 317 g of Intermediate 4 and the quantityof phosphorus pentoxide was reduced to 5 g. The product was a waxysolid, hereinafter called Surfactant 5.

EXAMPLE 6

The process of Example 4 was repeated except that the 317 g ofIntermediate 3 were replaced by 317 g of Intermediate 5 and the quantityof phosphorus pentoxide was reduced to 2.5 g. The product was a waxysolid, hereinafter called Surfactant 6.

EXAMPLE 7

115 g of Intermediate 3 were stirred at 60° C. and 8.83 g ofchlorosulphonic acid added gradually over 10 minutes. The mixture wasthen stirred for 16 hours at 65°-75° C. when the acid value was 45mg.KOH/g. The reaction mass was then discharged and allowed to solidifyto a waxy solid, hereinafter called Surfactant 7.

EXAMPLE 8

A blend of 390 g of Intermediate 6 and 13.37 g of monoethanolamine washeated with stirring in a round-bottom flask at 150° C. under anatmosphere of nitrogen for a period of 6 hours, water of reaction beingremoved via a Dean and Stark separator. At the end of this period 29.5 gof 83% phosphoric acid was added and stirring was continued at 40° C.for 3 hours, without removal of water of reaction.

The final product was a 98.1% solids solution of anionic surfactanthaving an acid value of 58.6 mg KOH/g, hereinafter called Surfactant 8.

EXAMPLE 9

The procedure of Example 8 was repeated, but using the followingreactants in place of those used in Example 8, 381.1 g ofpoly(12-hydroxystearic acid), 22.5 g of diethanolamine and 58.9 g of 83%phosphoric acid. The product was a 96.4% solids solution of anionicsurfactant having an acid value of 88.8 mg KOH/g hereinafter referred toas Surfactant 9.

EXAMPLE 10

The procedure of Example 9 was repeated, but replacing the 83%phosphoric acid by 47.2 g of 98% sulphuric acid and employing a reactiontemperature of 70° C. in the second stage. The product was a 96.3%solids solution of anionic surfactant having an acid value of 149.5 mgKOH/g, hereinafter referred to as Surfactant 10.

EXAMPLE 11

A blend of 300 g of poly(12-hydroxystearic acid) and 12.9 g of glycinewas heated with stirring at 200° C. under an atmosphere of nitrogen fora period of 6 hours, water of reaction being removed via a Dean andStark separator. The product was a 90.4% solids solution of anionicsurfactant having an acid value of 21.6 mg KOH/g, hereinafter calledSurfactant 11.

EXAMPLE 12

A blend of 300 g of poly(12-hydroxystearic acid) and 15.8 g of glycerolwas heated under an atmosphere of nitrogen for a period of 6 hours,water of reaction being removed as in Example 11. There was then added20.8 g of 83% phosphoric acid and heating was continued at 70° C. for 3hours without removal of water of reaction. The product was a 92.3%solids solution of anionic surfactant of acid value 53.1 mg KOH/g,hereinafter referred to as Surfactant 12.

EXAMPLE 13

A blend of 300 g of poly(12-hydroxystearic acid) and 20.9 g oftris(hydroxymethyl)aminomethane was heated with stirring for 6 hours at190° C. under an atmosphere of nitrogen, water of reaction being removedas in Example 11. There was then added 67.8 g of 83% phosphoric acid andheating was continued at 70° C. for 3 hours without removal of water ofreaction. The product was a 92.2% solids solution of anionic surfactanthaving an acid value of 130.8 mg KOH/g, hereinafter referred to asSurfactant 13.

EXAMPLE 14

A blend of 300 g of poly(12-hydroxystearic acid) and 13.1 g of glycollicacid was heated with stirring at 215° C. under a nitrogen atmosphere for6 hours, with removal of water of reaction. The product was a 95.7%solids solution of anionic surfactant of acid value 29.2 mg KOH/g,hereinafter referred to as Surfactant 14.

EXAMPLE 15

The process of Example 4 was repeated except that 105 g of Intermediate3 and 5 g of phosphorus pentoxide were used. The product was a waxysolid, hereinafter called Surfactant 15.

EXAMPLE 16

The process of Example 4 was repeated except that 317 g of Intermediate3 were replaced by 211 g of Intermediate 7. The product was a waxysolid, hereinafter called Surfactant 16.

EXAMPLE 17

The process of Example 4 was repeated except that the 317 g ofIntermediate 3 were replaced by 148 g of Intermediate 8. The product wasa waxy solid, hereinafter called Surfactant 17.

EXAMPLE 18

The process of Example 4 was repeated except that the 317 g ofIntermediate 3 were replaced by 100 g of Intermediate 9, and thequantity of phosphorus pentoxide was increased to 11.5 g. The productwas a soft waxy solid, hereinafter called Surfactant 18.

EXAMPLE 19

75.6 g of Intermediate 10 were stirred at room temperature and 10 g ofphosphorus pentoxide were added gradually over 30 minutes. Thetemperature was then raised to 90° C., and the reaction mass stirred fora further 16 hours at this temperature. It was then discharged and theproduct, a very viscous liquid, is hereinafter called Surfactant 19.

EXAMPLE 20

106 g of Intermediate 11 were stirred at 50°-55° C. and 5 g ofphosphorus pentoxide were added gradually over 45 minutes. Thetemperature was then raised to 90° C., and the reaction mass stirred fora further 4 hours at this temperature. It was then discharged and theproduct, a waxy solid, is hereinafter called Surfactant 20.

EXAMPLES 21 TO 44

The 24 dispersions, having the formulations described in Table 1 wereprepared by ball-milling the ingredients for 16 hours. All thedispersions were fluid and deflocculated, with pigment particles havinga mean diameter below 5 microns.

                  TABLE 1                                                         ______________________________________                                        Exam-              Surfactant  Organic liquid                                 ple   Pigment & amount                                                                           & Amount    & Amount                                       ______________________________________                                        21    Red 57:2  4.0 g  1    0.20 g   SBP3   5.80 g                            22    Red 57:2  4.0 g  1    0.20 g   Toluene                                                                              5.80 g                            23    Yellow 34 7.5 g  1    0.37 g   Xylene 2.13 g                            24    White 6   7.0 g  2    0.35 g   SBP3   2.65 g                            25    Yellow 34 7.0 g  2    0.35 g   SBP3   2.65 g                            26    Red 57:2  3.0 g  2    0.90 g   SBP3   6.10 g                            27    Yellow 34 7.0 g  3    0.35 g   MIBK   2.65 g                            28    White 6   7.0 g  3    0.35 g   2-EOEA 2.65 g                            29    Blue 15:3 2.5 g  1    0.50 g   SBP3   7.00 g                            30    Red 168   4.0 g  1    0.40 g   SBP3   5.60 g                            31    White 6   7.0 g  4    0.35 g   2-EOEA 2.65 g                            32    Yellow 42 7.0 g  4    0.35 g   MIBK   2.65 g                            33    White 6   5.0 g  15   0.25 g   TCE    4.75 g                            34    White 6   7.0 g  15   0.35 g   PA     2.65 g                            35    Red 101   6.0 g  5    0.3  g   BA     3.7  g                            36    White 6   5.0 g  6    0.35 g   PA     4.65 g                            37    White 6   6.0 g  7    0.3  g   BA     3.7  g                            38    Red 104   6.0 g  16   0.3  g   MOPA   3.7  g                            39    White 6   6.0 g  17   0.3  g   BA     3.7  g                            40    White 6   6.0 g  18   0.3  g   BA     3.7  g                            41    White 6   6.0 g  19   0.3  g   BA     3.7  g                            42    White 6   6.0 g  20   0.3  g   BA     3.7  g                            43    White 6   6.0 g  15   0.3  g   CH     3.7  g                            44    White 6   5.0 g  1    0.25 g   TCE    4.75 g                            ______________________________________                                         Abbreviations in Table 1                                                      SBP3 petroleum fraction boiling between 100 and 120° C.                MIBK methyliso-butyl ketone.                                                  2EOEA 2ethoxyethyl acetate.                                                   MOPA 1methoxy-2-propyl acetate.                                               TCE trichloroethylene.                                                        PA npropyl acetate.                                                           BA nbutyl acetate.                                                            CH cyclohexanone.                                                        

EXAMPLE 45

A dispersion was prepared according to the method of Example 21 usingthe following ingredients:

    ______________________________________                                        Pigment Blue 15:3 3.0 g                                                       Fluidising Agent 1                                                                              0.6 g                                                       Surfactant 1      0.3 g                                                       SBP3              6.1 g                                                       ______________________________________                                    

The dispersion was fluid and deflocculated with pigment particles havinga mean diameter below 5 microns.

EXAMPLES 46 TO 49

Four dispersions having the general formulation:

    ______________________________________                                        Dispersed Solid        80     g                                               Surfactant 1           4      g                                               EXSOL D 200/240        116    g                                               ______________________________________                                    

were prepared by bead milling the ingredients for 30 minutes with 1 mmglass beads using the solids listed in Table 2. All the dispersions werefluid and deflocculated with particles having mean diameters below 5microns. EXSOL D 200/240 is a mixed aliphatic/naphthenic solventavailable from Exxon Corporation and EXSOL is a trade mark.

                  TABLE 2                                                         ______________________________________                                        Example            Dispersed Solid                                            ______________________________________                                        46                 Flutriafen                                                 47                 Carbendazim                                                48                 Chlorothalonil                                             49                 Mancozeb                                                   ______________________________________                                    

EXAMPLE 50

A mixture of 2.0 g of Surfactant 8 and 178.0 g of diesel oil was heatedto 50° C. and stirred until it became homogeneous. To this solution wasadded 20.0 g of demineralised water whilst the total material was beingpassed through a "Silverson" mixer running at slow speed. When theaddition of the aqueous phase was complete, emulsification was continuedat full speed for 3 minutes.

The 10/90 water-in-oil emulsion thus obtained was of good stability,showing no more than slight oil separation and no water break afterstorage at room temperature for 24 hours.

EXAMPLE 51

A water-in-oil emulsion was prepared as described in Example 50 usingSurfactant 9 in place of Surfactant 8. The resulting emulsion was ofsimilar stability to that of Example 50.

EXAMPLE 52

A water-in-oil emulsion was prepared as described in Example 50, exceptthat, after dissolution of the product in the diesel oil and prior toemulsification, there was added to the aqueous phase 0.03 g of 0.880sp.gr. aqueous ammonia, bringing the pH of that phase to 7.0. Theresulting emulsion was of similar stability to that of Example 50.

EXAMPLE 53

A mixture of 1.0 g of Surfactant 11 and 4.0 g of ISOPAR L (anessentially iso-paraffinic hydrocarbon fraction: ISOPAR is a RegisteredTrade Mark) was heated to 70° C. and stirred until the mixture becamehomogeneous. This solution was then added slowly to 95.0 g ofdemineralised water whilst the total material was being passed through a"Silverson" mixer running at low speed. The mixer was then switched tofull speed and isopropylaminoethanol was added to the emulsion until thepH of the latter was brought to 9.2. Emulsification was then continuedat high speed for 3 minutes.

The resulting emulsion had good stability, showing only slight creamingat the surface after storage at room temperature for 24 hours.

EXAMPLE 54

Surfactant 12 was used to make an oil-in-water emulsion as described inExample 53, except that diesel oil was used in place of ISOPAR L and thepH of the oil phase after addition of isopropylaminoethanol was 9.7. Theresulting emulsion had good stability, showing only slight creaming atthe surface after storage at room temperature for 72 hours.

EXAMPLE 55

Surfactant 13 was used to make an oil-in-water emulsion as described inExample 54, except that the pH of the oil phase after addition ofisopropylaminoethanol was 8.7. The resulting emulsion had similarstability to that of Example 54.

EXAMPLE 56

A mixture of 1.15 g of Surfactant 14 and 4.0 g of paraffinic mineral oilwas heated to 70° C. and stirred until the mixture was homogeneous. Thisoil phase was then emulsified into 95 g of demineralised water asdescribed in Example 53, the pH of the oil phase after addition ofisopropylaminoethanol being 9.7. The resulting emulsion was of similarstability to that of Example 54.

EXAMPLE 57

The 90.4% solids solution of Surfactant 11 was used to prepare a 10/90water-in-oil emulsion according to the procedure described in Example50. The resulting emulsion had similar stability to that of Example 50.

EXAMPLE 58

A water-in-oil emulsion was prepared as described in Example 50, butreplacing the Surfactant 8 by Surfactant 10, replacing the demineralisedwater by 20.0 g of 20% aqueous calcium chloride solution, and reducingthe amount of diesel oil to 176.0 g.

The resulting emulsion showed similar stability to that of Example 50.

EXAMPLE 59

A water-in-oil emulsion was prepared as described in Example 50 usingSurfactant 8, but replacing the demineralised water by 20.0 g of a 20%aqueous calcium chloride solution and adding thereto, prior toemulsification, 0.05 g of 0.880 sp.gr. aqueous ammonia.

The resulting emulsion had similar stability to that of Example 50.

EXAMPLES 60 TO 63

Mixtures of magnetic material, Surfactant 4, resin and solvent, asindicated in Table 3, were premixed using a high-speed stirrer and thensubjected to a high energy ball-milling for the time shown in Table 3.Dispersions suitable for use in the manufacture of magnetic media wereobtained in this way.

The magnetic materials used were as follows:

Type A A gamma-Fe₂ O₃ with a surface area of 18.5 m² /g, an oilabsorption of 41 ml/100 g and a particle length of 0.4 microns. This istypical of magnetic iron oxides used in audio tapes.

Type B A cobalt-doped gamma-Fe₂ O₃ with a surface area of 23 m² /g, anoil absorption of 41 g/100 g and a particle length of 0.35 microns. Thismaterial which was supplied by Bayer UK Ltd. under the product nameBAYFERROX AC 5120M (BAYFERROX is a trade mark) is typical of magneticiron oxides used in high-bias audio tapes and in video cassette tapes.

Type C A stabilised magnetite with a surface area of 19 m² /g, an oilabsorption of 40 g/100 g, and a particle length of 0.45 microns. Thismaterial was supplied by Bayer UK Ltd., under the product name BAYFERROXAC 5110M.

Type D A chromium dioxide magnetic material of the type used in computertapes and video cassette tapes.

The resin was a hydroxylated vinyl chloride/vinyl acetate copolymerobtained from Union Carbide under the trade mark UCAR VAGH.

In the following tables the following abbreviations are used

THF is tetrahydrofuran.

MEK is methyl ethylketone.

                  TABLE 3                                                         ______________________________________                                                         Amount   Sol-          High                                         Magnetic  of       vent(s)       energy                                       material  Surfac-  and    Amount milling                               Example                                                                              & Amount  tant 4   Amount of resin                                                                             time                                  Number (g)       (g)      (g)    (g)    (minutes)                             ______________________________________                                        60     Type A    0.8      THF 9.3                                                                              0.6    60                                           20.0               MEK 9.3                                             61     Type B    0.8      THF 9.3                                                                              0.6    60                                           20.0               MEK 9.3                                             62     Type C    0.8      THF 9.3                                                                              0.6    60                                           20.0               MEK 9.3                                             63     Type D    0.8      THF 9.3                                                                              0.6    60                                           20.0               MEK 9.3                                             ______________________________________                                    

EXAMPLES 60A TO 63A

Each dispersion prepared in Examples 60 to 63 was let down to a lacquerwith a 20% w/w solution of a polyurethane (PU) resin in tetrahydrofuran.Typically, the let down was carried out in three stages withapproximately equal quantities of PU resin solution each time. Eachmixture was subjected to a 5 minute high-energy ball milling after eachstage of the let down. The resultant lacquer was then further let downwith solvent and the mixture subjected to a further 5 minuteshigh-energy ball milling. Table 4 identifies the dispersions, theweights of PU resin solution and of solvent used in the let down; thelet down solvent was a 1:1 mixture of tetrahydrofuran andmethylethylketone. The PU resin used was obtained from B. F. GoodrichInc. under the name ESTANE 5701-F1 (ESTANE is a trade mark).

                  TABLE 4                                                         ______________________________________                                        Example            Amount of                                                  or CE   Dispersion 20% PU resin                                                                              Amount of solvent                              Number  used       solution (g)                                                                              used (g)                                       ______________________________________                                        60A     Ex. 60     22          14.92                                          61A     Ex. 61     22          14.92                                          62A     Ex. 62     22          14.92                                          63A     Ex. 63     22          14.92                                          ______________________________________                                    

Magnetostatic Evaluations

Each lacquer was discharged from the ball-mill and used to coat to rollof 12 micron thick biaxially-oriented polyester film.

The coating was carried out using a mechanised wire-wound K-bar (MeyerBar) draw-down system. The K-bar was calibrated to leave a wet film ofthickness 50 microns. The machine was modified so that a powerfulpermanent magnet mounted about 1.5 cm above the polyester film followedthe motion of the K-bar. In this way a strong magnetic field passedacross the wet-film before any appreciable solvent evaporation had takenplace. The film was then allowed to dry by solvent evaporation.

Samples of coated films were then evaluated by conventional techniqueson a vibrating-sample magnetometer. Table 5 reports the magneticparameters of coated films determined by this evaluation technique.

The magnetic parameters determined were coercivity (in Oersteds),squareness (Br/Bs) and Magnetic Orientation Ratio (OR). Coercivity andsquareness are parallel to the direction of travel of the magnet overthe film.

                  TABLE 5                                                         ______________________________________                                        Example  Coercivity  Squareness                                                                              Orientation                                    Number   (Oersteds)  (Br/Bs)   Ratio                                          ______________________________________                                        60A      426         0.79      2.30                                           61A      678         0.76      1.82                                           62A      450         0.58      1.08                                           63A      765         0.63      1.33                                           ______________________________________                                    

We claim:
 1. A compound of the formula:

    MOSO.sub.2 --(O--B--CO).sub.m --X--D.sup.1

wherein M is a cation; B is alkylene, alkenylene, cycloalkylene orpolycycloalkylene, each containing from 3 to 24 carbon atoms with atleast 3 carbon atoms directly between the --O-- and --CO-- groups and isunsubstituted or substituted by a chloro, hydroxy, amino or alkoxy; m isfrom 2 to 75; X is O or NR; R is H, alkyl, alkenyl, cycloalkyl orphenyl; and D¹ is selected from the group consisting of H, a hydrocarbongroup and a hydrocarbon group substituted by chloro, hydroxy, amino oralkoxy containing up to 50 carbon atoms.
 2. A compound according toclaim 1 wherein:M is H⁺, an alkali metal cation or an ammonium ion; B isC₅₋₂₀ -alkylene or C₅₋₂₀ -alkenylene; m is a number from 2 to 75; X is Oor NR in which R is H, C₁₋₅ -alkyl or C₁₋₅ -alkenyl; and D¹ is selectedfrom the group consisting of alkyl, alkenyl, hydroxyalkyl,hydroxyalkenyl, cycloalkyl or polycycloalkyl containing up to 35 carbonatoms.
 3. A compound of the formula:

    MOSO.sub.2 --(O--B--CO).sub.m --D

wherein m is a cation, B is a hydrocarbon group m is from 2 to 75; and Dis the residue of an alcohol, primary amine secondary amine, or D₁ --XRin which, D₁ is an aliphatic or alicyclic group; X is O or NR; and R isH, alkyl, alkenyl, cycloalkyl or phenyl.
 4. A compound according toclaim 3 wherein each of B and D₁ contain up to 50 carbon atoms.
 5. Acompound according to claim 3 wherein B contains at least 3 carbonatoms.
 6. A compound according to claim 3 wherein B is alkylene oralkenylene containing from 5 to 20 carbon atoms.
 7. A compound accordingto claim 3 wherein D₁ is alkyl or alkenyl containing up to 35 carbonatoms.
 8. A compound according to claim 3 wherein D¹ is selected fromthe group consisting of methyl, ethyl, decyl, dodecyl, hexadecyl andoctadecyl.
 9. A compound according to claim 3 wherein B is selected fromthe group consisting of pentamethylene, 1-octylnon-1,9-ylene,1-hexyl-undec-1,11-ylene, 1-nonyl-oct-1,8-ylene and1-hexyl-dodec-3-en-1,12-ylene.
 10. A dispersible or emulsifiablecomposition of:(1) (a) a solid selected from the group consisting ofpigments, fillers, dyestuffs, optical brightening agents, magneticmetal, magnetic oxides, solids for oil-based and invert-emulsiondrilling muds, biocides, agrochemicals and pharmaceuticals; or (b) awater-immiscible organic liquid, and (2) a compound according to claim 1or claim
 3. 11. A compound of the formula:

    MOSO.sub.2 --(O--B--CO).sub.m --O--D

wherein: M is a cation; B is a substituted or unsubstituted alkylene,alkenylene, cycloalkylene or polycycloalkylene group of ahydroxycarboxylic acid residue having at least 3 and not more than 50carbon atoms and

    (O--B--CO).sub.m --O--D

forms a polyester which can be derived from a hydroxycarboxylic acid ofthe formula:

    HO--B--COOH

and a monohydric alcohol of formula D--OH; D is an alcohol residue; andm is 2 to 75.